Vat dyestuffs



Patented Sept. 11, 1951 I VAT DYESTUFFS Eduard Moergell, Neuewelt, near Basel, Switzerland, asslgnorte Giba. Limited, Basel, Switzerland, a Swiss- No Drawing. Application June 20,, 1949, Serial In Switzerland July 1, 1948 .6 Qlgirns, (Q1. 260-316) present ment on rela es va of the anthraquinone series more innit enchyet e estufis twoanthm- W nucle intemoene ed h-Y e s a hezple w ich e commonly re e red o nis'flml hlai; tqflihflm w I i OPE? P! the t9 p es d vne cyestuifie o the and seri s which san ine va uab sha e missed I9: cellualpsic v. il en a d seed to w t as wel an -other ble properties. 1 iihe is leased o the ebserx on t a we d es u ercnmduced when an a c'fl em which substituted i at ast-9m 14, weesitian y a xthpefluemhenzc emiw were, is rea te w h serhazolie ie agentsrsm' di th im de er ng s S ar n terials for the present process can he produced in the known manner for example by condensing together a 1-aminoanthraquinone and a, l-haloilmfllrfiqlll mlfi In this reac on the a thr eumone components must h s9 s ect that a mane. andif desired r se er H e in a anther .e-nosit on-by an o th i 7 imylamino roup- In th nrqdli mn 9f $1 fi thrimide it is of p t cular welle fluorine tom oi he e hoeflu ben q lemin anew Qnthe-ne tion to the rbenyl g o p i stable even in the presence oi popper and =m rs ts which as n o he expected 1mm 2. reference to the work of Qovaert, cclremisches Zentral'platt 19.39 191- I. page 8 As mvac ples ,o -ha sen t :ag!fl qn wit mthe-iiuorebenzwlamino grou a .be menl-chloIro-A-and .l-chlorp-t-(ortho-nuoro- 'wa aminoi .-an hvra.q1iin ne.- As l-amlncenmmquinones with ortho .fluOIQhfiMQYMIllZQ there ar m cem c erexamnle l-eniino- 4- and 1-amino-5-(orthoefiuorobenzo lami l anthraquinone.

By condensation of such components together there are obtained azd-dianthrimides which are esubstituted inieach anthraquinone residue by an orthoi-fluorobenzoyla nino group.

When there arenondensed with the above po mponents i-aminoanthraquinones or l-halogenanthraquinones respectively, which contain no prtho-fluorobenzoylamino groups, for example 1-- am n thracuinone h hloma h gul n itse f. or such components con ain a sub i umt ldifi le t r m the o thmflucm ewxlami group, ezd-dianthrimides are obtained v winch an crt eefluem enz yiamin g ou i an i-Qm mmnmmtna w ich gil 'efil} a a,

o kp siizi m 0 at. EPW111121? e we? in; tem ssh;

ei nts 5 In ac ordan e with men on d en hrim ee obtained as des the fact as to 9 9, both A contain fluorine, the app H p; mides which contain only one penzoylamino group, the application 01' aluminum chloride is eil'ective, in which case in knownmanner dilpents of organic nature such as pyridine or nitrobenzene may be present in the reaction, or also the application of aluminum chloride-sulphur dioxide addition products.

The products obtained according tothe present process constitute va'iuable vat dyestuits. Phey can be employed by customary methods or the dyeing and printing'of -the"most-vanied fibers of animal and in .of vegetable nature. includ W091 s lk and na u a c tt 1 "an; s

en. artificia Z811 and ce lu o e wo mm- 9- .se et d cel ules members "I has indeed al e dy been emi for th manu actur Q1 ve item *9 a yl t wa a th same? Wham-t nses? s ic 291415 nd i als aliases? i own tha e ub titu ion i a thp-aos t u t the i q r a is with ne .qrbmmine in m nxee e ts is disn ecemei c 11. 1 .99 .91 shes ic a mm- ;It wa ,;l 1 owever, no to be expected that by rebi l-aminoanthraquinone, 20 parts of sodium carbonate, 1 part each of cuprous chloride and copper acetate and 20 parts by volume of nitrobenzene is stirred for 16 hours at 200-205 C. Aiter cooling, the reaction product is filtered with suction, washed with nitrobenzene and alcohol and treated t l s te hy o i -e dio r ove! '01 the inorganic "salts,f---being thereupon washed with water and dried. The 5-(ortho-fluorobenzoylamlno) -1'.1-dianthrimide is obtainedin good yield as a uniform red crystal powder. 1

For the carbazole ring" closure parts of the dianthr'imide are stirred for 24 hoursat' 'infa solution'of 36 'parts'of aluminum chloride, 2

parts by volume of orthofluorobenzoyl chloride and 100 parts by volume of nitrobenzene; The

' 'reaction'product is poured into amixture of ice andfhy drochloric acid and after addition of 5 parts ot'sodium perborate the whole is stirred'for "dissolves in;concentrated sulphuric acid with a bluevcoloruand dyes otton irom a yellow brown vatin bright fast yellow shades,

V V rammple'a I A miirt ure of (ii -partsv of l-aniino-S-(or'tho- .fiuoro-benzoylamino)-anthraquinone, 6.4 parts of l chloro-5-(ortho-fluorobenzoylam-ino) -anthraquinoned parts of sodium carbonate, 0.2 part eachof .cuprous chloride" and'copper' acetate and i 70 parts bygvolume. 0f nitrobe'nzeneis' stirred'for l hours at;205 C. 'Afterjworking up as described in-Example there is obtained the 5:5'di-(ortho- .fiuorobenzoylaminm l;1'-dianthrimide as a red brown crystal powder in excellent yield. 7

With stirring 10.4 parts oi the dianthrimide thus obtained are. introduced into 100 parts of 92 per cent. sulphuric acid'. .The whole is stirred then for 18 hours 70 is filtered and washed until ,ne'utral. "I tldyes for timers at at room temperature. .oln a'test portion under the microscope there canith'en'be recognized a crystal mixture consisting of long yellow and --shapeless olive crystals, (If crystallisation has mot take nlecve-ithesp u on Shquld be carefully lowed to rise'to about 25 C.

diluted with ya sulphuric acid of lower concentrai tion.) The crystal mixture is filtered with suction. washed with a little percent. and then with 85 per cent. sulphuric acid and then introduced into ice water containing sodium nitrate,

and stirred until a bright yellow color is produced. The product is; then "filtered; and the-l residue washed with water untilme'utral dried.

The dyestuff of the formula which isa yellow powder, dissolves in concen-, 20 trated'sulphuric acid with a blue color and dyes vegetable fiber from a brown hydr0- su1phite vat in powerful, clear, golden yellow shadesjiof very good ia'stnessproperties. I If there is employed for the production or the 25 dianthrimide instead of l-amino-fi-(ortho fluoro- ,ben'zoylamino) '-anthraquinone the "equivalent quantity of l-amino-5-benzoylamino-anthraquinone, there is obtained the fi-benzolyamino-li (ortho fiuorobenzoylamino) '-lzl"-dianthrimide', which by the method described yields a carba'zole derivative which dyes in somewhat more reddish golden yellow shades. l 5

'The 1-chloro-5-(ortho-fluorobenzoylamirio) anthraquinone'is' obtained by acylation of 1--chloro-5-amino anthraquinone withortho-fluoroben z'oyl chloride, for examplein ortho dich'lorobenzene at'boiling temperature. It crystallizes from the solvent in yellow crystals and melts at 230- j 30. 5 C. (uncorrflc d). .l; Example 3:

"'11' parts of l-chloro-d-(ortho-fiuorobenzoyl aminoll anthraquinone, 9 parts of L-amind-E- benzoylarninoanthraquinone; '5- parts of sodium "carbonate; '0'. 5 parteach-of cuprous chloride and copper acetate-and 100 parts by volume ofnitrobenzene ar'e stirred for 16 hoursat ZOO-205 216. Working up is carried out'as described in Exaniie 1 and there is obtained in good yieldanid 'purity the 5-benzoylamino df-(ortho fluorobenzoylamino) '1 :1 dianthrimide as a" a-dark br'own 'crystal-powderk 5 parts offthediiahthiiihide are stirred for-3 hours at 33-36 C. in 100 parts of per cent.

55 sulphuric acid. The reaction product is' poured parts of sodium perborate added and the'whole I then stirred overnight and thetemperatureai- The dyestufi of the formula v the fiber from a brown hydrosulphite vatf'after hanging in the air, in brown shades of excel e'nt fa'stness properties.

B'y replacing Jthej l-amino-5-benzoylaminoamino 5-(ortho fluorobenzoylaniino) -anthraquinone a carbazole dyestufl is obtained which yields dye shades displaced towards yellow-brown.

1 chloro 4 (ortho fiuorobenzoylamino) anthraquinone is obtained by acylation of 1- chloro-4-aminoanthraquinone with ortho-fiuorobenzoyl chloride. It crystallizes from ortho-dichlorobenzene in yellow crystals and melts at 214.5-215" C. (uncorrected).

Example 4 1 part of the dyestufi obtained according to the first and second paragraphs of Example 2 is vatted at 50 C. in 100 parts of water with the addition of 2 parts of sodium hydrosulphite and 4 parts by volume of caustic soda solution of 36 B. The stock vat thus obtained is added to a solution of 2 parts of sodium hydrosulphite and 4 parts by volume of caustic soda solution of 36 B. in 2000 parts of water. In the dyebath thus produced 100 parts of cotton are dyed in 1 hour at 45-50 C. with the addition of 10 parts of sodium chloride. The cotton is thereupon squeezed out,

oxidized in the air, rinsed, acidified, rinsed again 00 and soaped at the boil. It becomes dyed in powerful golden yellow shades.

The term vat dyestuffs of the aIa'-dianthrimide carbazole type as appearing in the claims is to be understood as excluding compounds containing more than two anthraquinone skeleton or any condensed ring system other than that of the a:a-dianthrimide carbazole of the formula Having thus disclosed the invention, what is claimed is:

1. A vat dyestufi of the uzd-dianthrimide 10 group.

3. The vat dyestuff of the formula 4. The vat dyestuff of the formula 5. The vat dyestufi of the formula NH N H- C 0 6. The vat dyestuff of the formula EDUARD MOERGELI.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,856,207 Bruns et a1 May 3, 1932 2,284,062 Mieg et al May 26, 1942 FOREIGN PATENTS Number Country Date 138,236 Switzerland May 1, 1930 592,268 Great Britain Sept. 12, 1947 

1. A VAT DYESTUFF OF THE A:A''-DIANTHRIMIDE CARBAZOLE TYPE WHEREIN AT LEAST ONE FURTHER APOSITION OF THE TWO ANTHRAQUINONE NUCLEI IS OCCUPIED BY AN ORTHO-FLUOROBENZOYLAMINO GROUP. 